Plumban

Plumban
Imena
	IUPAC ime Plumban
	Druga imena plumban, svinčev tetrahidrid, tetrahidrosvinec, svinčev(IV) hidrid
Identifikatorji
Številka CAS	15875-18-0;
3D model (JSmol)	Interaktivna slika;
ChEBI	CHEBI:30181;
ChemSpider	109888;
PubChem CID	123278;
	InChI InChI=1S/Pb.4H Key: XRCKXJLUPOKIPF-UHFFFAOYSA-N; InChI=1/Pb.4H/rH4Pb/h1H4 Key: XRCKXJLUPOKIPF-BJORFFIVAF;
	SMILES [Pb];
Lastnosti
Kemijska formula	PbH4
Molska masa	211,23 g/mol
Vrelišče	−13 °C (9 °F; 260 K)
	Če ni navedeno drugače, podatki veljajo za material v standardnem stanju pri 25 °C, 100 kPa).
	Sklici infopolja

Plumban je kovinski hidrid s kemijsko formulo PbH₄ in ena od 14 svinčevih spojin z vodikom.^[1] Plumban ni niti dobro znan niti dobro opisan. Je termodinamično nestabilen in zlahka odceplja vodik.^[2] Derivata plumbana str svinčev tetrafluorid (PbF₄) in tetraetilsvinec ((CH₃CH₂)₄Pb).

Zgodovina uredi

Do nedavnega ni bilo zanesljivo znano, ali je bil plumban kdaj dejansko sintetiziran,^[3] čeprav prva poročila o sintezi segajo v dvajseta leta 20. stoletja.^[4] Leta 1963 sta Saalfeld in Svec poročala, da sta odkrila PbH₄ z masno spektrometrijo.^[5] Plumban je bil večkrat predmet Dirac-Hartree-Fockove relativistične kalkulacijske študije, ki je raziskovala stabilnosti, geometrije in relativne energije hidridov s formulo MH₄ ali MH2.^[2]^[6]^[7]

Lastnosti uredi

Plumban je nestabilen brezbarven plin, najtežji iz skupine IV hidridov.^[8] Ima tetraedrično (T_d) zgradbo z ravnotežno razdaljo med svincem in vodikom 1,73 Å.^[9] Formalni oksidacijski stanji vodika in svinca sta -1 and +4, ker je elektronegativnost vodika višja od elektronegativnosti svinca. Stabilnost kovinskih hidridov s formulo MH₄ (M = C do Pb) z naraščakočim vrstnim številom kovine pada.

Priprava uredi

Zgodnje študije PbH₄ so pokazale, da je molekula nestabilna v primerjavi z njenimi lažjimi analogi (silan, german in stanan).^[10] Plumban se ne more sintetizirati po postopkih za sintezo germana (GeH₄) in stanana (SnH₄).

Leta 1999 so plumban sintetizirali iz svinčevega(II) nitrata (Pb(NO₃)₂) in natrijevega borohidrida NaBH₄.^[11] Leta 2005 so poročali o nenascentnem mehanizmu za sintezo plumbana.^[12]

Leta 2003 sta Wang in Andrews skrbno preučila pripravo PbH4 z lasersko ablacijo in prepoznala njegove infrardeče (IR) pasove.^[13]

Sklici uredi

↑ Porritt, C.J. (1975). Chem. Ind-London. 9: 398.
↑ ^2,0 ^2,1 Hein, Thomas A.; Thiel, Walter; Lee, Timothy J. (1993). "Ab initio study of the stability and vibrational spectra of plumbane, methylplumbane, and homologous compounds". The Journal of Physical Chemistry. 97 (17): 4381–4385. doi: 10.1021/j100119a021. hdl: 11858/00-001M-0000-0028-1862-2.
↑ Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochman, M. Advanced Inorganic Chemistry. Wiley: New York, 1999.
↑ Paneth, Fritz; Nörring, Otto (1920). "Über Bleiwasserstoff". Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 53 (9): 1693–1710. doi: 10.1002/cber.19200530915.
↑ Saalfeld, Fred E.; Svec, Harry J. (1963). "The Mass Spectra of Volatile Hydrides. I. The Monoelemental Hydrides of the Group IVB and VB Elements". Inorganic Chemistry. 2: 46–50. doi: 10.1021/ic50005a014.
↑ Desclaux, J.P.; Pyykko, P. (1974). "Relativistic and non-relativistic Hartree-Fock one-centre expansion calculations for the series CH4 to PbH4within the spherical approximation". Chemical Physics Letters. 29 (4): 534–539. Bibcode:1974CPL....29..534D. doi:10.1016/0009-2614(74)85085-2.
↑ Pyykkö, P.; Desclaux, J.P. (1977). "Dirac–Fock one-centre calculations show (114)H4 to resemble PbH4". Nature. 266 (5600): 336–337.Bibcode: 1977Natur.266..336P. doi:10.1038/266336a0.
↑ CRC Handbook of Chemistry and Physics. Online Edition.
↑ Visser, O.; Visscher, L.; Aerts, P. J. C.; Nieuwpoort, W. C. (1992). "Relativistic all-electron molecular Hartree-Fock-Dirac-(Breit) calculations on CH₄, SiH₄, GeH₄, SnH₄, PbH₄". Theoretica Chimica Acta. 81 (6): 405–416.doi:10.1007/BF01134864.
↑ Malli, Gulzari L.; Siegert, Martin; Turner, David P. (2004). "Relativistic and electron correlation effects for molecules of heavy elements: Ab initio fully relativistic coupled-cluster calculations for PbH4". International Journal of Quantum Chemistry. 99 (6): 940–949. doi:10.1002/qua.20142.
↑ Krivtsun, V. M.; Kuritsyn, Y. A.; Snegirev, E. P. (1999). "Observation of IR absorption spectra of the unstable PbH4 molecule" (PDF). Opt. Spectrosc. 86 (5): 686–691. Bibcode:1999OptSp..86..686K. Arhivirano iz izvirnika (PDF) 4. marca 2016. Pridobljeno 31. decembra 2012.
↑ Zou, Y; Jin, FX; Chen, ZJ; Qiu, DR; Yang, PY (2005). "Non-nascent hydrogen mechanism of plumbane generation". Guang Pu Xue Yu Guang Pu Fen Xi = Guang Pu. 25 (10): 1720–3. PMID 16395924.
↑ Wang, Xuefeng; Andrews, Lester (2003). "Infrared Spectra of Group 14 Hydrides in Solid Hydrogen: Experimental Observation of PbH₄, Pb₂H₂, and Pb₂H₄". Journal of the American Chemical Society. 125 (21): 6581–6587.doi:10.1021/ja029862l. PMID 12785799.

[1] Porritt, C.J. (1975). Chem. Ind-London. 9: 398.

[ref2-2] 2,0 ^2,1 Hein, Thomas A.; Thiel, Walter; Lee, Timothy J. (1993). "Ab initio study of the stability and vibrational spectra of plumbane, methylplumbane, and homologous compounds". The Journal of Physical Chemistry. 97 (17): 4381–4385. doi: 10.1021/j100119a021. hdl: 11858/00-001M-0000-0028-1862-2.

[ref3-3] Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochman, M. Advanced Inorganic Chemistry. Wiley: New York, 1999.

[4] Paneth, Fritz; Nörring, Otto (1920). "Über Bleiwasserstoff". Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 53 (9): 1693–1710. doi: 10.1002/cber.19200530915.

[5] Saalfeld, Fred E.; Svec, Harry J. (1963). "The Mass Spectra of Volatile Hydrides. I. The Monoelemental Hydrides of the Group IVB and VB Elements". Inorganic Chemistry. 2: 46–50. doi: 10.1021/ic50005a014.

[6] Desclaux, J.P.; Pyykko, P. (1974). "Relativistic and non-relativistic Hartree-Fock one-centre expansion calculations for the series CH4 to PbH4within the spherical approximation". Chemical Physics Letters. 29 (4): 534–539. Bibcode:1974CPL....29..534D. doi:10.1016/0009-2614(74)85085-2.

[7] Pyykkö, P.; Desclaux, J.P. (1977). "Dirac–Fock one-centre calculations show (114)H4 to resemble PbH4". Nature. 266 (5600): 336–337.Bibcode: 1977Natur.266..336P. doi:10.1038/266336a0.

[8] CRC Handbook of Chemistry and Physics. Online Edition.

[9] Visser, O.; Visscher, L.; Aerts, P. J. C.; Nieuwpoort, W. C. (1992). "Relativistic all-electron molecular Hartree-Fock-Dirac-(Breit) calculations on CH₄, SiH₄, GeH₄, SnH₄, PbH₄". Theoretica Chimica Acta. 81 (6): 405–416.doi:10.1007/BF01134864.

[10] Malli, Gulzari L.; Siegert, Martin; Turner, David P. (2004). "Relativistic and electron correlation effects for molecules of heavy elements: Ab initio fully relativistic coupled-cluster calculations for PbH4". International Journal of Quantum Chemistry. 99 (6): 940–949. doi:10.1002/qua.20142.

[11] Krivtsun, V. M.; Kuritsyn, Y. A.; Snegirev, E. P. (1999). "Observation of IR absorption spectra of the unstable PbH4 molecule" (PDF). Opt. Spectrosc. 86 (5): 686–691. Bibcode:1999OptSp..86..686K. Arhivirano iz izvirnika (PDF) 4. marca 2016. Pridobljeno 31. decembra 2012.

[12] Zou, Y; Jin, FX; Chen, ZJ; Qiu, DR; Yang, PY (2005). "Non-nascent hydrogen mechanism of plumbane generation". Guang Pu Xue Yu Guang Pu Fen Xi = Guang Pu. 25 (10): 1720–3. PMID 16395924.

[13] Wang, Xuefeng; Andrews, Lester (2003). "Infrared Spectra of Group 14 Hydrides in Solid Hydrogen: Experimental Observation of PbH₄, Pb₂H₂, and Pb₂H₄". Journal of the American Chemical Society. 125 (21): 6581–6587.doi:10.1021/ja029862l. PMID 12785799.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]